AU2003290188B2 - Method for making an abrasion resistant steel plate and plate obtained - Google Patents
Method for making an abrasion resistant steel plate and plate obtained Download PDFInfo
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- AU2003290188B2 AU2003290188B2 AU2003290188A AU2003290188A AU2003290188B2 AU 2003290188 B2 AU2003290188 B2 AU 2003290188B2 AU 2003290188 A AU2003290188 A AU 2003290188A AU 2003290188 A AU2003290188 A AU 2003290188A AU 2003290188 B2 AU2003290188 B2 AU 2003290188B2
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- 229910000831 Steel Inorganic materials 0.000 title claims description 51
- 239000010959 steel Substances 0.000 title claims description 51
- 238000000034 method Methods 0.000 title claims description 18
- 238000005299 abrasion Methods 0.000 title claims description 14
- 239000010936 titanium Substances 0.000 claims description 47
- 229910052719 titanium Inorganic materials 0.000 claims description 36
- 229910052799 carbon Inorganic materials 0.000 claims description 26
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 22
- 229910000734 martensite Inorganic materials 0.000 claims description 20
- 229910052726 zirconium Inorganic materials 0.000 claims description 18
- 229910001566 austenite Inorganic materials 0.000 claims description 17
- 150000001247 metal acetylides Chemical class 0.000 claims description 14
- 229910052750 molybdenum Inorganic materials 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 230000000717 retained effect Effects 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 238000007669 thermal treatment Methods 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 229910052715 tantalum Inorganic materials 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052711 selenium Inorganic materials 0.000 claims description 4
- 229910052714 tellurium Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 238000005098 hot rolling Methods 0.000 claims description 3
- 229910052745 lead Inorganic materials 0.000 claims description 3
- 239000002893 slag Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 238000005496 tempering Methods 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 238000003303 reheating Methods 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 claims 1
- 239000004576 sand Substances 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 18
- -1 titanium carbides Chemical class 0.000 description 11
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000010955 niobium Substances 0.000 description 6
- 230000009466 transformation Effects 0.000 description 6
- 239000011651 chromium Substances 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 229910001563 bainite Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000011669 selenium Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 208000020442 loss of weight Diseases 0.000 description 1
- UMUKXUYHMLVFLM-UHFFFAOYSA-N manganese(ii) selenide Chemical class [Mn+2].[Se-2] UMUKXUYHMLVFLM-UHFFFAOYSA-N 0.000 description 1
- ZLANVVMKMCTKMT-UHFFFAOYSA-N methanidylidynevanadium(1+) Chemical class [V+]#[C-] ZLANVVMKMCTKMT-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical class [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000011044 quartzite Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000004772 tellurides Chemical class 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/18—Hardening; Quenching with or without subsequent tempering
- C21D1/19—Hardening; Quenching with or without subsequent tempering by interrupted quenching
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/001—Austenite
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/002—Bainite
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/008—Martensite
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
Description
P: PER\PHFf 12612070 =nrd do~-3/I 2/2l00 00 -1- METHOD FOR MAKING AN ABRASION-RESISTANT STEEL PLATE AND PLATE
OBTAINED
00 The present invention relates to an abrasion-resistant steel and its production 00 5 method.
SAbrasion-resistant steels are well known and are generally steels having great Shardness (of from 400 to 500 Brinell), having a martensitic structure and containing from 0.12% to 0.3% of carbon. It is generally taken that, in order to increase the wear- Sresistance, it is simply necessary to increase the hardness, but that is done to the detriment of other properties, such as, for example, suitability for welding or forming by bending. In order to obtain steels having both very good wear-resistance and good suitability for use, therefore, means other than increasing the hardness have been sought.
Thus, it has been proposed in EP 0527 276 and US 5,393,358 to improve the abrasion-resistance of a steel which contains from 0.05% to 0.45% of carbon, up to 1% of silicon, up to 2% of manganese, up to 2% of copper, up to 10% of nickel, up to 3% of chromium and up to 3% of molybdenum, boron, niobium and vanadium, by adding from 0.015% to 1.5% of titanium, in order to form coarse titanium carbides. That steel is quenched and consequently comprises a martensitic structure, the increase in abrasionresistance being obtained by the presence of coarse titanium carbides. However, more particularly when the steel is cast in bars, that improvement is limited because, under the effect of abrasive stresses, the carbides become separated and no longer serve their purpose. Furthermore, in those steels, the presence of coarse titanium carbides inhibits ductility. Consequently, plates produced with those steels are difficult to flatten and bend, which limits their possible uses.
The object of the present invention is to overcome those disadvantages by providing an abrasion-resistant steel plate which has good surface evenness and which, all things otherwise being equal, has abrasion-resistance which is better than that or known steels.
To that end, the invention relates to a method for producing a steel workpiece, for example plate steel, which is resistant to abrasion, whose chemical composition comprises by weight: 0.35% C 0.8% 0% Si 2% P: OPER\PHIl 2612070 amnd d.-312/1~00 00
O
0-2- 0% AI <2% 0.35% Si AI 2% 0% Mn 0 0% Ni 00 5 0% Cr S0% Mo 0.50% iN 0% <W 1.00% 0 0.1% Mo +W/2 0.50% rC 0% <Cu 0% B 0.02% 0% Ti 2% 0% Zr 4% 0.05% Ti Zr/2 2% 0% S 0.15% N 0.03% optionally at least one element selected from Nb, Ta and V at contents such that Nb/2 Ta/4 V optionally at least one element from Se, Te, Ca, Bi, Pb at contents which are less than or equal to 0.1%, the balance being iron and impurities resulting from the production operation, the chemical composition further complying with the following relationships, with C* C Ti/4 Zr/8 7xN/8: 0.10% C* 0.55% and: Ti Zr/2 7xN/2 0.05% and: 1.05xMn 0.54xNi +0.50xCr 0.3x(Mo W/2) 1 12 K 1.8, or more advantageously 2 with: K 0.5 if B 0.0005% and K 0 if B 0.0005%; according to which the workpiece is subjected to a thermal treatment carried out from a hot-forming temperature, such as the temperature of hot rolling, or after austenitization by reheating in a furnace, the thermal treatment comprising: -cooling the workpiece at an average cooling rate greater than 0.5 0 C/s between a temperature greater than AC 3 and a temperature of from T 800 270xC* 90xMn P:OPER\PlI\ 12612070 nmlnd do:-3/12/200 00 O-3- S37xNi 70xCr 83x(Mo W/2) to T-50 0 C, the temperature being expressed in °C and the contents of Mn, Ni, Cr, Mo and W being expressed as by weight, then cooling the workpiece at a mean core cooling rate Vr 1150xep 1 7 (in and 00 greater than 0.1°C/s between the temperature T and 100 0 C, ep being the thickness of 00 5 the plate expressed in mm, O then cooling the workpiece to ambient temperature, a flattening treatment optionally being carried out after the thermal treatment.
SThe thermal treatment may optionally be followed by tempering at a temperature of CN less than 350°C, and preferably less than 250*C.
The invention also relates to a steel workpiece produced by a method as described in the immediately preceding paragraph.
The invention further relates to a steel workpiece, for example plate steel, having a composition as described in the method of the invention and a structure which is constituted by from 5% to 20% retained austenite with carbides, the remainder of the structure being martensitic or martensitic/bainitic. When the workpiece is a plate, its thickness may be from 2 mm to 150 mm. The flatness of the workpiece is characterized by a deflection which is less than or equal to 12 mm/m, and preferably less than 5 mm/m.
When the carbon content is such that: 0.1% C Ti/4 Zr/8 7xN/8 0.2%, the Brinell hardness is preferably from 280 HB to 450 HB.
When the carbon content is such that: 0.2% C Ti/4 Zr/8 7xN/8 0.3%, the Brinell hardness is preferably from 380 HB to 550 HB.
When the carbon content is such that: 0.3% C Ti/4 Zr/8 7xN/8 the Brinell hardness is preferably from 450 HB to 650 HB.
The invention will now be described in greater detail, but in a non-limiting manner, and illustrated with reference to examples.
In order to produce plate according to the invention, a steel is produced whose chemical composition comprises, in by weight: from 0.35% to 0.8% of carbon, and preferably more than 0.45%, or more than and from 0% to 2% of titanium, from 0% to 4% of zirconium, these contents having to be such that: 0.05% Ti+Zr/2 The carbon is intended, firstly, to achieve a sufficiently hard martensitic structure and, secondly, to form titanium and/or zirconium carbides. The total Ti+Zr/2 must be greater than 0.05%, preferably greater than 0.10%, and, more advantageously still, greater than 0.3%, or even greater than so that there is a minimum of carbides formed, but must remain less than and preferably less than or equal to because above that level the toughness and the suitability for use are inhibited.
From 0% (or trace levels) to 2% of silicon and from 0% (or trace levels) to 2% of aluminium, the total Si+AI being from 0.35% to 2% and preferably being greater than and more advantageously still greater than Those elements, which are deoxidants, further have the effect of promoting the production of a metastable retained austenite which is heavily charged with carbon and whose transformation into martensite is accompanied by a large expansion promoting the anchoring of the titanium carbides.
From 0% (or trace levels) to 2% or even 2.5% of manganese, from 0% (or trace levels) to 4% or even 5% of nickel and from 0% (or trace levels) to 4% or even of chromium, in order to obtain an adequate level of quenchability and to adjust the various mechanical characteristics or characteristics of use. Nickel has in particular an advantageous effect on the toughness, but that element is expensive. Chromium also forms fine carbides in martensite or bainite.
From 0% (or trace levels) to 0.50% of molybdenum. That element increases the quenchability and forms, in martensite or bainite, fine hardening carbides, in particular by precipitation owing to auto-tempering during cooling. It is not necessary to exceed a content of 0.50% in order to obtain the desired effect, in particular with regard to the precipitation of hardening carbides. Molybdenum can be replaced, completely or partially, with twice the weight of tungsten.
Nevertheless, this substitution is not desirable in practice because it does not provide any advantage over molybdenum and is more expensive.
Optionally, from 0% to 1.5% of copper. That element can bring about an additional hardening without inhibiting the weldability. Above a level of it no longer has any significant effect, leads to hot-rolling difficulties and is needlessly expensive.
From 0% to 0.02% of boron. That element can be added optionally in order to increase the quenchability. So that that effect is obtained, the content of boron must preferably be greater than 0.0005%, or more advantageously 0.001%, and does not need to exceed substantially 0.01%.
Up to 0.15% of sulphur. That element is a residue which is generally limited to 0.005% or less, but its content may be voluntarily increased in order to improve machinability. It should be noted that, in the presence of sulphur, in order to prevent difficulties concerning transformation in the hot state, the content of manganese must be greater than 7 times the content of sulphur.
Optionally, at least one element selected from niobium, tantalum and vanadium at contents such that Nb/2+Ta/4+V remains less than 0.5% in\order to form relatively coarse carbides which improve the resistance to abrasion. However, the carbides formed by those elements are less effective than those formed by titanium or zirconium and, for that reason, they are optional and added in a limited quantity.
Optionally, one or more elements selected from selenium, tellurium, calcium, bismuth and lead at contents of less than 0.1% each. Those elements are intended to improve machinability. It should be noted that, when steel contains Se and/or Te, the content of manganese must be such, taking into consideration the content of sulphur, that manganese selenides or tellurides can form.
The balance being iron and impurities resulting from the production operation.
The impurities include in particular nitrogen whose content depends on the production method, but generally does not exceed 0.03%. That element can react with titanium or zirconium to form nitrides which must not be too coarse in order not to inhibit the toughness. In order to prevent the formation of coarse nitrides, titanium and zirconium may be added to the liquid steel in a very progressive manner, for example, by placing in contact with the oxidized liquid steel an oxidized phase, such as a slag charged with titanium or zirconium oxides, then deoxidizing the liquid steel in order to cause the titanium or zirconium to diffuse slowly from the oxidized phase to the liquid steel.
Furthermore, in order to obtain satisfactory properties, the contents of carbon, titanium, zirconium and nitrogen must be such that: 0.1% C Ti/4 Zr/8 7xN/8 0.55%.
The expression C Ti/4 Zr/8 7xN/8 C* represents the content of free carbon after precipitation of the titanium and zirconium carbides, taking into P. OPER\PHM12612070 aulcd do:-3/12/2008 00
O
-6- Sconsideration the formation of titanium and zirconium nitrides. That free carbon content C* must be greater than and preferably greater than or equal to 0.22%, in order to have martensite having a minimum hardness, but above 0.55% the toughness and suitability for oO use are excessively inhibited.
00 5 The chemical composition must further be selected so that the quenchability of the 0 steel is sufficient, taking into consideration the thickness of the plate which it is desirable to NC produce. To that end, the chemical composition must comply with the following Srelationship: rC Quench =1.05xMn 0.54xNi +0.50xCr 0.3x(Mo W/2) 12 K 1.8 or more advantageously 2 with: K 0.5 if B or equal to 0.0005% and K 0 if B 0.0005%.
It should be noted that, more particularly when Quench is from 1.8 to 2, it is preferable for the content of silicon to be greater than 0.5% in order to promote the formation of retained austenite.
Furthermore, the contents of Ti, Zr and N must preferably be such that: Ti Zr/2 7xN/2 0.05% and more advantageously greater than and even more advantageously greater than so that the content of carbides is sufficient.
Finally and in order to obtain good abrasion resistance, the micrographic structure of the steel is constituted by martensite or bainite or an admixture of those two structures and from 5% to 20% of retained austenite, that structure further comprising coarse titanium or zirconium carbides, or niobium, tantalum or vanadium carbides, which are formed at high temperature. The inventors have established that the effectiveness of coarse carbides for improving abrasion resistance could be inhibited by the premature separation thereof and that that separation could be prevented by the presence of metastable austenite which is transformed into new martensite under the effect of the abrasion phenomena. Since the transformation of the metastable austenite into new martensite is brought about by expansion, that transformation in the abraded sub-layer increases the resistance to separation of the carbides and, in that manner, improves the abrasion resistance.
Furthermore, the great hardness of the steel and the presence of embrittling titanium carbides make it necessary to limit insofar as possible the flattening operations.
From that point of view, the inventors established that, by slowing down the cooling sufficiently in the region of bainitic/martensitic transformation, the residual deformations of the products are reduced, which allows flattening operations to be limited. The inventors established that, by cooling down the workpiece or the plate at a cooling rate Vr P:'OPER\PHHI12612070 amnnddo-3/12 002 -7- S1150xep' 1 7 (in this formula, ep is the thickness of the plate expressed in mm and the cooling rate is expressed in below a temperature T 800 270xC* 90xMn -37xNi 70XCr 83x(Mo (expressed in OC), firstly, the production of a significant 00 proportion of residual austenite was promoted and, secondly, the residual stresses brought 0 0 5 about by the phase changes were reduced.
SIn order to produce a very planar plate which has good abrasion resistance, the C steel is produced and cast in the form of a slab or bar. The slab or bar is hot-rolled in order 0to obtain a plate which is subjected to thermal processing which allows both the desired CN structure and good surface evenness to be obtained without further flattening or with limited flattening. The thermal processing may be carried out directly in the rolling heat or carried out subsequently, optionally after cold-flattening or flattening at a medium temperature.
In order to carry out the thermal processing operation: the steel is heated above the AC 3 point in order to confer on it a completely austenitic structure, then, it is cooled at a mean cooling rate greater than the critical bainitic transformation rate as far as a temperature which is equal to or slightly less than (by more than approximately 50C) a temperature T 800 270xC* 90xMn -37xNi 70XCr 83x(Mo W/2) (expressed in then, the plate is cooled, between the temperature defined in this manner (that is to say, approximately from T to T 50°C) and approximately 100°C, at a mean core cooling rate Vr of from 0.1°C/s, in order to obtain sufficient hardness, to 1150xep' 7 in order to obtain the desired structure, and the plate is cooled as far as ambient temperature, preferably but without being compulsory, at a slow rate.
Furthermore, it is possible to carry out a stress-relief processing operation at a temperature less than or equal to 350°C, and preferably less than or equal to 250°C.
In this manner, a plate is obtained whose thickness can be from 2 mm to 150 mm and which has excellent surface evenness, characterized by a deflection which is less than 12 mm per metre without flattening or with moderate flattening. The plate has a hardness of from 280HB to 650HB. That hardness depends principally on the content of free carbon C* C Ti/4 Zr/8 7xN/8.
In accordance with the contents of free carbon it is possible to define a plurality of ranges corresponding to levels of increasing hardness, and in particular: a) 0.1% C* the hardness is approximately from 280HB to 450HB, b) 0.2% C* the hardness is approximately from 380HB to 550HB, c) 0.3% C* the hardness is approximately from 450HB to 650HB.
Since the hardness is a function of the content of free carbon the same hardness can be obtained with very different contents of titanium or zirconium. With equal hardness, the abrasion resistance becomes higher as the content of titanium or zirconium becomes greater. Similarly, with an equal content of titanium or zirconium, the abrasion resistance improves as the hardness becomes greater. Furthermore, using the steel becomes easier as the content of free carbon decreases, but with an equal content of free carbon, the ductility improves as the content of titanium decreases. All those considerations allow the contents of carbon and titanium or zirconium to be selected that lead to all the properties which are most suitable for each field of application.
According to the hardness levels, the uses are, for example: from 280 to 450 HB: scoops, skips for lorries and dump trucks, cyclone shielding, hoppers, moulds for aggregates, from 380 to 550 HB: shielding for impact grinders, bulldozer blades, grab bucket blades, grills for sieves, from 450 to 650 HB: plates for shielding cylinder type grinders, reinforcement elements for scoops, reinforcement elements under leading blades, cut-water blade shields, leading edges.
By way of example, steel plates designated A to G according to the invention and H to J according to the prior art are considered. The chemical compositions of the steels, expressed in 10 3 by weight, as well as the hardness, the content of residual austenite of the structure and a wear resistance value Rus are summarized in Table 1.
Table 1 C Si Al Mn Ni Cr Mo W Ti B N HB aust Rus A 360 850 50 1300 500 700 100 500 400 2 6 460 10 1.42 B 640 850 50 400 1500 700 110 450 620 3 7 555 14 2.72 C 590 520 570 550 320 1850 470 540 7 570 12 2.24 D 705 460 630 1090 280 2450 430 100 825 7 580 13 3.14 E 690 370 25 740 310 2100 460 795 6 605 10 2.83 F 350 810 30 1200 270 1350 380 160 2 6 510 8 1.32 G 390 790 35 1210 250 1340 390 405 3 6 495 11 1.77 H 340 380 30 1260 470 820 370 410 3 6 475 1 0.86 I 315 330 25 1230 180 1360 395 165 2 6 515 2 0.7 J 367 315 30 1215 210 1375 405 430 2 5 500 2 1.01 The wear resistance value Rus varies as the inverse logarithm of the loss of weight of a prismatic test piece which is rotated in a container containing graded quartzite aggregate.
All the plates have a thickness of 30 mm and the plates corresponding to steels A to G have been quenched in accordance with the invention, .after austenitization at 900 0
C.
After austenitization, the cooling conditions are: for the plates of steel B and D: cooling at a mean rate of 0.7°C/s above temperature T defined above and at a mean rate of 0.13°C/s therebelow, in accordance with the invention; for plates of steel A, C, E, F, G: cooling at a mean rate of 6 0 C/s above temperature T defined above and at a mean rate of 1.4°C/s therebelow, in accordance with the invention; for the plates of steel H, I, J, given by way of comparison: austenitization at 900 0 C, followed by cooling at a mean rate of 20°C/s above temperature T defined above, and at a mean rate of 12 0 C/s therebelow.
The plates according to the invention have a martensitic/bainitic structure which contains from 5% to 20% of retained austenite, whereas the plates given by way of comparison have a completely martensitic structure, that is to say, martensitic and not containing more than 2 or 3% of retained austenite. All the plates contain carbides.
A comparison of the wear resistances shows that, with a similar hardness and content of titanium, the plates according to the invention have a coefficient Rus which is on average 0.5 greater than that of the plates according to the prior art. In particular, comparison of examples A and H which substantially differ in terms of the structure (content of residual austenite of 10% for A, completely martensitic structure for H) shows the incidence of the presence of residual austenite in the structure. It should be noted that the difference in content of residual austenite results from both the difference between the thermal processing operations and the difference between the contents of silicon.
It can further be observed that, all things substantially being equal otherwise, the contribution to the wear resistance which can be attributed to the titanium carbides is significantly higher when their presence is combined with that of residual austenite in accordance with the invention than when those carbides are precipitated within a matrix which is substantially free from residual austenite. Thus, for similar differences in the contents of titanium (and therefore of TiC, the carbon still being in excess), the pair of steels F,G (according to the invention) differ distinctly from the pair of steels I,J in terms of increase in resistance brought about by the titanium. For F,G, the increase in resistance Rus brought about by 0.245% of Ti is 0.46, whereas it is only 0.31 for a difference of 0.265% of Ti in the case of the pair I,J.
That observation can be attributed to the increased squeezing effect on the titanium carbides by the surrounding matrix when it contains residual austenite which can be transformed into hard martensite with expansion under the effect of the abrasive stresses.
Furthermore, the deformation after cooling, without planishing, for the steel plates according to the invention is less than 10mm/m and is approximately 15mm/m for the steel plate H.
In practice, that leads either to the possibility of supplying the products without planishing, or carrying out planishing in order to comply with stricter requirements in terms of surface evenness (for example, 5mm/m), but which is carried out more readily and with fewer stresses being introduced owing to the lesser original deformation of the products according to the invention.
P %OPER\PIII2612070 -ncd do. -3/I 200 00
O
O -11- Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", and variations such as "comprises" and "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps 00 but not the exclusion of any other integer or step or group of integers or steps.
00 5 The reference in this specification to any prior publication (or information derived from Sit), or to any matter which is known, is not, and should not be taken as an acknowledgment Sor admission or any form of suggestion that that prior publication (or information derived from it) or known matter forms part of the common general knowledge in the field of r endeavour to which this specification relates.
Claims (18)
1. Method for producing a workpiece of steel which is resistant to abrasion and which 00 has a chemical composition, by weight of: 00 5 0.35% C 0.8% 0% Si 2% C1 0% Al 2% S0.35% Si Al 2% N 0% Mn 0% Ni 0% Cr 0% Mo 0.50% 0% <W 1.00% 0.1% Mo +W/2 0.50% 0% B 0.02% 0% Ti 2% 0% Zr 4% 0.05% Ti Zr/2 2% 0% S 0.15% N 0.03% -optionally from 0% to 1.5% of copper, Soptionally at least one element selected from Nb, Ta and V at contents such that Nb/2 Ta/4 V -optionally at least one element selected from Se, Te, Ca, Bi, Pb at contents which are less than or equal to 0.1%, the balance being iron and impurities resulting from the production operation, the chemical composition further complying with the following relationships: 0.1% C Ti/4 Zr/8 7xN/8 0.55% and: Ti Zr/2 7xN/2 0.05% and: 1.05xMn 0.54xNi +0.50xCr 0.3x(Mo W/2) 1 12 K 1.8 with K 0.5 if B 0.0005% and K 0 if B 0.0005%, according to which the workpiece is subjected to a thermal treatment carried out from a P:OPER\PHIEH2612070 amend doc-3/12/2008 00 0 -13- Shot-forming temperature or after austenitization by reheating in a furnace, the thermal treatment comprising: O -cooling the workpiece at an average cooling rate greater than 0.5 0 C/s between a 00 temperature greater than AC 3 and a temperature of from T 800 270xC* 90xMn 00 5 37xNi 70XCr 83x(Mo with C* C Ti/4 Zr/8 7xN/8, to T-50 0 C, then cooling the workpiece at a core cooling rate Vr 1150xep 17 and greater than ri 0.1 0 C/s between the temperature T and 100 0 C, ep being the thickness of the plate Sexpressed in mm, C then cooling the workpiece to ambient temperature.
2. Method according to claim 1, wherein the workpiece is plate steel.
3. Method according to claim 1 or 2, wherein the hot-forming temperature is the temperature of hot rolling.
4. Method according to any one of claims 1 to 3, wherein the workpiece is subjected to a flattening treatment. Method according to any one of the preceding claims, wherein: 1.05xMn 0.54xNi +0.50xCr 0.3x(Mo W/2) 1 2 K 2.
6. Method according to any one of the preceding claims, wherein: C 0.45%.
7. Method according to any one of the preceding claims, wherein: Si Al
8. Method according to any one of the preceding claims, wherein: Ti Zr/2 0.10%.
9. Method according to any one of the preceding claims, wherein: Ti Zr/2 0.30%. Method according to any one of the preceding claims, wherein: P \OPER\PH12612070 amend d:-3/12/2008 00 -14- SC* 0.22%. 0
11. Method according to any one of the preceding claims, wherein a tempering o0 treatment is carried out, at a temperature less than or equal to 350 0 C, after the thermal 00 5 treatment. C 12. Method according to any one of the preceding claims, wherein, in order to add Cc Stitanium to the steel, molten steel is placed in contact with a titanium-containing slag and Cl the titanium is caused to diffuse slowly from the slag into the molten steel.
13. Method according to claim 1 and substantially as herein described.
14. A steel workpiece produced by a method according to any one of the preceding claims. Workpiece of steel which is resistant to abrasion and whose chemical composition comprises, by weight: 0.35% C 0.8% 0% Si 2% 0% Al 2% 0.35% Si Al 2% 0% Mn 0% Ni 0% Cr 0% Mo 0.50% 0% W 1.00% 0.1% Mo +W/2 0.50% 0% B 0.02% 0% Ti 2% 0% Zr 4% 0.05% Ti Zr/2 2% 0% S 0.15% N 0.03% -optionally from 0% to 1.5% of copper, P.OPER\PiHl f2612070 nld doc.3/12/2008 a Q- optionally at least one element selected from Nb, Ta and V at contents such that Nb/2 Ta/4 V optionally at least one element selected from Se, Te, Ca, Bi, Pb at contents less than 00 or equal to 0.1%, 0 0 5 the balance being iron and impurities resulting from the production operation, the chemical Scomposition further complying with the following relationships: C 0.1% C Ti/4 Zr/8 7xN/8 0.55% tc, Sand: "N Ti Zr/2 7xN/2 0.05 and: 1.05xMn 0.54xNi +0.50xCr 0.3x(Mo W/2) 1 2 K 1.8 with: K 0.5 if B 0.0005% and K 0 if B 0.0005%, wherein the flatness of the workpiece has a deflection of less than 12mm/m and the steel has a martensitic or martensitic/bainitic structure and further comprises from 5% to retained austenite and carbides.
16. Workpiece according to claim 15, wherein: 1.05xMn 0.54xNi +0.50xCr 0.3x(Mo W/2) 1 2 K 2.
17. Workpiece according to claim 15 or claim 16, wherein: C 0.45%.
18. Workpiece according to any one of claims 15 to 17, wherein: Si Al
19. Workpiece according to any one of claims 15 to 18, wherein: Ti Zr/2 0.10%. Workpiece according to any one of claims 15 to 19, wherein: Ti Zr/2 0.30%.
21. Workpiece according to any one of claims 15 to 20, wherein: C* 0.22%. P: OPER\PIIII2612070 dlcnd doe-3/12/200 00 S-16- U
22. Workpiece according to any one of claims 15 to 21, which is plate steel.
23. Workpiece according to claim 22, wherein the plate steel has a thickness of from 2 Smm to 150 mm. OO 00 S24. Workpiece according to any one of claims 15 to 23, having a Brinell hardness from CN 280 HB to 450 HB when 0.1% C Ti/4 Zr/8 7xN/8 from 380 HB to 550 HB Swhen 0.2% C Ti/4 Zr/8 7xN/8 or from 450 HB to 650 HB when 0.3% C CN Ti/4 Zr/8 7xN/8 A steel workpiece substantially as herein described with reference to the Examples, excluding the Comparative Examples.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR02/14424 | 2002-11-19 | ||
| FR0214424A FR2847270B1 (en) | 2002-11-19 | 2002-11-19 | METHOD FOR MANUFACTURING AN ABRASION RESISTANT STEEL SHEET AND OBTAINED SHEET |
| PCT/FR2003/003359 WO2004048620A1 (en) | 2002-11-19 | 2003-11-13 | Method for making an abrasion resistant steel plate and plate obtained |
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| AU2003290188A1 AU2003290188A1 (en) | 2004-06-18 |
| AU2003290188B2 true AU2003290188B2 (en) | 2009-01-08 |
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| AU2003290188A Expired AU2003290188B2 (en) | 2002-11-19 | 2003-11-13 | Method for making an abrasion resistant steel plate and plate obtained |
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| Country | Link |
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| US (3) | US7459041B2 (en) |
| EP (1) | EP1563104B1 (en) |
| JP (1) | JP4535877B2 (en) |
| KR (1) | KR101010570B1 (en) |
| CN (1) | CN100350061C (en) |
| AR (1) | AR042071A1 (en) |
| AT (1) | ATE400667T1 (en) |
| AU (1) | AU2003290188B2 (en) |
| BR (2) | BR122013002046B8 (en) |
| CA (1) | CA2506351C (en) |
| DE (1) | DE60322092D1 (en) |
| ES (1) | ES2309377T3 (en) |
| FR (1) | FR2847270B1 (en) |
| PE (1) | PE20040487A1 (en) |
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| RU (1) | RU2327802C2 (en) |
| SI (1) | SI1563104T1 (en) |
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| US5108518A (en) * | 1989-12-18 | 1992-04-28 | Sumitomo Metal Industries, Ltd. | Method of producing thin high carbon steel sheet which exhibits resistance to hydrogen embrittlement after heat treatment |
| EP0527276A1 (en) * | 1990-06-06 | 1993-02-17 | Nkk Corporation | An abrasion resistant steel |
| US5393358A (en) * | 1990-12-03 | 1995-02-28 | Nkk Corporation | Method for producing abrasion-resistant steel having excellent surface property |
| JPH09249935A (en) * | 1996-03-13 | 1997-09-22 | Sumitomo Metal Ind Ltd | High strength steel material excellent in sulfide stress cracking resistance and its production |
| US6080247A (en) * | 1997-02-21 | 2000-06-27 | Gs Technologies Operating Company | Comminuting media comprising martensitic/austenitic steel containing retained work-transformable austenite |
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- 2003-11-13 US US10/535,418 patent/US7459041B2/en active Active
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| US5108518A (en) * | 1989-12-18 | 1992-04-28 | Sumitomo Metal Industries, Ltd. | Method of producing thin high carbon steel sheet which exhibits resistance to hydrogen embrittlement after heat treatment |
| EP0527276A1 (en) * | 1990-06-06 | 1993-02-17 | Nkk Corporation | An abrasion resistant steel |
| US5393358A (en) * | 1990-12-03 | 1995-02-28 | Nkk Corporation | Method for producing abrasion-resistant steel having excellent surface property |
| JPH09249935A (en) * | 1996-03-13 | 1997-09-22 | Sumitomo Metal Ind Ltd | High strength steel material excellent in sulfide stress cracking resistance and its production |
| US6080247A (en) * | 1997-02-21 | 2000-06-27 | Gs Technologies Operating Company | Comminuting media comprising martensitic/austenitic steel containing retained work-transformable austenite |
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